Organometallic compositions useful as lubricating oil additives

ABSTRACT

This invention provides novel organometallic compositions represented by the general formula: ##STR1## wherein M is selected from the group consisting of members of Groups IIa, IIb, IIIa, IVa and VIIb of the Periodic System of Elements; R 1  is selected from the group consisting of radicals represented by the formula ##STR2## wherein R 2  is selected from the group consisting of hydrogen, hydrocarbyl radicals and heteroatom-substituted hydrocarbyl radicals wherein said heteroatoms are selected from the group consisting of halogen, oxygen, sulfur, nitrogen and phosphorus atoms; R 3  is selected from the group consisting of hydrogen and lower alkyl radicals; R is selected from the group consisting of hydrocarbyl radicals and hetero atom-substituted derivatives thereof wherein said heteroatoms are selected from the group consisting of halogen, oxygen, sulfur, nitrogen and phosphorus atoms; and v, w, x, y and z are integers. Said novel compositions are useful as additives to lubricating oils to provide rust inhibition, sludge dispersant, wear reduction and anti-oxidant properties.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to organometallic compositions useful asadditives to lubricating oils to impart increased rust inhibition,sludge dispersant, wear reduction and anti-oxidant properties thereto.

2. Summary of the Art

Various metal chelating agents are known for solubilizing metals innonaqueous systems. For example, in U.S. Pat. No. 4,387,244, a class ofsuch chelating agents are disclosed which are synthesized by (1)reacting formaldehyde and an amino acid and (2) by reacting theresulting product, with a phenol. The metal chelating agent may be inthe acid form or the alkali metal or ammonium salt thereof. Thechelation of Cu(II) and Fe(III) ions with this chelating agent isspecifically disclosed and while it is claimed that other metal ions maybe chelated therewith, the identity of such other metals is not found inthe patent. (It is reported in a trade brochure, published on one of theindividual metal chelating agents, disclosed in this patent, that nickeland cobalt may be complexed.) The chelation of metal ions other thanCu(II) and Fe(III) with other chelating agents may be found in U.S. Pat.Nos. 4,069,249; 4,152,345 and 4,225,502; however the chelating agents ofthese patents are structurally different than the chelating agent ofU.S. Pat. No. 4,387,244 and it is well known that the degree ofchelating ability of chelating agents is not predictable a priori fromthe chemical structure of the chelating agent alone.

Organometallic additives are many times incorporated into lubricatingoils to provide lubricating compositions having special and improvedproperties. For example certain copper and lead compounds impartcorrosion resistance to lubricating oils. Organoboron compounds provideextreme pressure, anti-wear and friction reducing properties. Organozinc compounds are also known wear reducing additives. However, thedetermination of whether an organometallic compound will "work", thatis, will impart the desired properties when added to a lubricating oilis also unpredictable with a reasonable degree of certainty from thechemical structure of such organometallic compound alone.

Therefore, it is one object of this invention to provide novelorganometallic compounds that are useful as lubricating oil additives.

It is another object of this invention to provide additives that improvethe rust inhibition, oxidative stability, wear properties, etc. oflubricating oils.

It is another object of this invention to provide lubricating oilcompositions having improved corrosion and wear properties and stabilityto oxidation.

Additional objects, advantages and features of the invention will becomeapparent to those skilled in the art from the following description.

SUMMARY OF THE INVENTION

The present invention provides novel compositions of matter representedby the general formula: ##STR3## wherein M is selected from the groupconsisting of members of Groups IIa, IIb, IIIa, IVa and VIIb of thePeriodic System of Elements; R¹ is selected from the group consisting ofradicals represented by the formula ##STR4## wherein R² is selected fromthe group consisting of hydrogen, hydrocarbyl radicals andheteroatom-substituted hydrocarbyl radicals wherein said heteroatoms areselected from the group consisting of halogen, oxygen, sulfur, nitrogenand phosphorus atoms; R₃ is selected from the group consisting ofhydrogen and lower alkyl radicals; R is selected from the groupconsisting of hydrocarbyl radicals and hetero atom-substitutedderivatives thereof wherein said heteroatoms are selected from the groupconsisting of halogen, oxygen, sulfur, nitrogen and phosphorus atoms;and v, w, x, y and z are integers. x is an integer which represents thedegree of polymerization or oligimerization of the organic reactantsthat are combined to provide the organo chelate of the compositions ofthis invention, i.e. the organo chelate is represented by that portionwithin the outer brackets of the above general formula. y represents thenumber of metal ions chelated by the organo portion of the above novelcompositions and w is an integer of 0 or 1 but at least one w must be 1if x is 0. v is an integer representing the number of organo chelatemoieties coordinated with a single M. z represents the valence of themetal ion M.

Preferably the metal ion M is selected from the group consisting of Mg,Ca, Ba, Zn, Al, Pb and Mn.

The novel compositions, wherein M is a magnesium or barium ion providelubricating oil compositions having unexpectedly improvedrust-inhibition properties. When the metal ion is manganese ion, anadditive that imparts unexpectedly improved dispersant properties tolubricating oils is obtained. Moreover, when the metal ion is selectedfrom the group consisting of Mg, Zn, Mn and Ca, a novel compositionwhich imparts unexpectedly improved wear reduction properties tolubricating oil compositions is obtained. Finally when the metal ion isselected from the group consisting of Mg, Mn and Ca, a novel compositionis obtained which imparts unexpectedly improved oxidative stability whencombined with a lubricating oil.

Thus, it is clear that the novel compositions of the instant inventionmay be used as lubricating oil additives to impart desired properties tolubricating oils. Moreover, certain of the novel compositions of theinstant invention impart a plurality of improved properties tolubricating oil compositions.

DETAILED DESCRIPTION OF THE INVENTION

The invention is directed to novel compositions of matter represented bythe general formula: ##STR5## wherein M is selected from the groupconsisting of members of Groups IIa, IIb, IIIa, IVa and VIIb of thePeriodic System of Elements; R¹ is selected from the group consisting ofradicals represented by the formula ##STR6## wherein R² is selected fromthe group consisting of hydrogen, hydrocarbyl radicals andheteroatom-substituted hydrocarbyl radicals wherein said heteroatoms areselected from the group consisting of halogen, oxygen, sulfur, nitrogenand phosphorus atoms; R is selected from the group consisting ofhydrocarbyl radicals and hetero atom-substituted derivatives thereofwherein said heteroatoms are selected from the group consisting ofhalogen, oxygen, sulfur, nitrogen and phosphorus atoms R₃ is selectedfrom the group consisting of hydrogen and lower alkyl radicals, e.g.methyl and ethyl radicals; and x, y and z are integers. Preferably xranges from 0 to about 25, more preferably from about 1 to about 15,e.g. 2 to about 6. y represents the number of metal ions included in theabove compositions and preferably ranges from 1 to about 30, morepreferably from about 1 to about 10, e.g. from 1 to 5. z represents thevalence of the metal ion and ranges from 1 to 6, preferably from 1 to 3,e.g. 2. In general, the product of y and z will approach the value of x,i.e. the organo portion of the novel composition is utilized to itsmaximum chelating ability, but the product of x and y may be much lowerthan x and still provide compositions having good lubricating oiladditive properties. w is an integer of 0 or 1 but at least one w mustbe 1 if x is 0. v represents the number of organo chelate moietiescoordinated with a single M and varies from 1 to 6, preferably from 1 to3, e.g. 1 or 2.

In the above composition M is preferably selected from the groupconsisting of Mg, Ca, Ba, Zn, Al, Pb and Mn. The individual metal ionmay be selected on the basis of the desired end use properties for thenovel composition. For example, as noted above, if the novel compositionis to be utilized as a dispersant additive for lubricating oils, M ispreferably Mn, and so forth.

In the above composition R is preferably selected from the groupconsisting of hydrocarbyl radicals having from 1 to 1000 carbon atoms,more preferably from 3 to 75 carbon atoms, and most preferably fromabout 3 to 15 carbon atoms, e. g. 8 or 9 carbon atoms. Thus R mayrepresent a radical selected from the group consisting of n-propyl,isopropyl, n-butyl, isobutyl, n-octyl, n-nonyl, n-dodecyl,2,3-dimethyl-hexyl, n-octadecyl, 3,3-dimethyltetradecyl,3-phenyl-2,4-diethylhexyl.

For hydrocarbon solubility, R may be a polyisobutyl, poly-n-butyl orpolypropyl radical having a molecular weight of from about 300 to about14,000. Radicals resulting from the copolymerization of mixtures of C₂to C₆ olefins and diolefins, e.g. ethylene, propylene, iso-butylene,etc., having a molecular weight of from about 100 to about 15,000 arealso suitable for the compositions of this invention.

In the composition of the present invention R² may be selected from thegroup consisting of hydrogen, a lower alkylgroup, having from 1 to about6 carbon atoms, ##STR7##

When the novel compositions are used as additives in lubricating oils,the R, R² and to some extent the R³ groups will be selected to providethe requisite solubility in the lubricating oil of choice. For example,when the lubricating oil is a hydrocarbon the number of carbon atoms ineither or both R and R² will generally be greater than when apolyalkylene glycol lubricating oil is the choice. It is generallypreferred, when selecting a hydrocarbon-soluble composition of thepresent invention, to increase the number of carbon atoms on the R group(to promote hydrocarbon solubility) rather than the R² group since bulkyR² groups may interfere with the chelating efficiency of the adjacentcarboxyl group.

The compositions of this invention may be prepared in a three stepreaction procedure. In the first step, formaldehyde is reacted with anamino acid of the general formula H₂ NCR² R³ COOH in a basic aqueoussolution. For example, the pH of the solution may be maintained at fromabout 7.5 to about 8.0 with sodium or potassium hydroxide or other basicmaterial to provide a first product. In the second step, the firstproduct is reacted with a phenolic compound to provide a second product.For example, while continuing to maintain the pH at from about 7.5 toabout 8.0, a methanol solution of a phenol of the general formula##STR8## may be slowly added to the first product, and the resultingmixture heated to reflux to thereby provide said second product. Uponcooling and standing, the second product may be separated out as an oilylayer while a water and methanol layer is decanted. Said second productis usually obtained as a sodium or potassium salt depending on the basicmaterial utilized in the first step. The second product may be dried andground to a powder. Vacuum drying is suitable but other types may beemployed.

In the third step of the reaction, the second product contacted with thedesired metal ion in solution to exchange said metal ion for the sodiumor potassium ion and thereby obtain the composition of the presentinvention. The contacting may be carried out in a nonaqueous solution,i.e. n-butylether, or any other solvent which will dissolve at least aportion of the second product and a salt of the metal ion. Theefficiency of the reaction between the second product and the metal saltmay be conveniently increased by carrying out the contacting underconditions of reflux. A suitable temperature range for effecting thethird step of the reaction is from 100° to 200°, preferably from 100° to145° C. The time for contracting the product of the second step with themetal ion may range from 1 to 12 hours, preferably from 1 to 4 hours.

The compositions of the present invention are conveniently separatedfrom the nonaqueous solvent by water washing to separate residualmetals. The washed mixture is then vacuum distilled to remove excesssolvent and the composition of the invention recovered.

It will be appreciated from the above reaction scheme that R¹ is theresidue resulting from the alpha-amino acid and R² and R³ represent thealpha substituents thereof. For example, if the amino acid used isglycine, R² and R³ =H; if alanine is used, R² =CH₃ -and R³ =H, etc. R₃is limited to hydrogen and lower alkyl radicals; however R² is notlimited but may also be selected from the groups of substituentsconsisting of hydroxylalkyl, thioalkyl, phenylalkyl, and other groups.By way of illustration, the following list contains various R²substituents which are deemed to be within the scope of the presentinvention, as well as the name of the amino acid from which thesubstituents is obtained:

    ______________________________________                                        R.sup.2 =                                                                     ______________________________________                                        H                glycine                                                      CH.sub.3         alanine                                                      CH.sub.3 CH.sub.2                                                                              alpha-amino butyric acid                                     CH.sub.3 CH.sub.2 CH.sub.2                                                                     (R.sup.3 = CH.sub.3) iso-leucine acid                        (CH.sub.3).sub.2CHCH.sub.2                                                                     leucine                                                      CH.sub.3 CH.sub.2 CH(CH.sub.3)                                                                 2-amino-3-methyl-pentanoic acid                              HOCH.sub.2       serine                                                       CH.sub.3 CH(OH)  threonine                                                    HSCH.sub.2       cysteine                                                     CH.sub.3SCH.sub.2 CH.sub.2                                                                     methionine                                                   H.sub.2 NCOCH.sub.2                                                                            asparagine                                                   H.sub.2 NCOCH.sub.2 CH.sub.2                                                                   glutamine                                                    HOOCCH.sub.2     aspartic acid                                                HOOCCHCH.sub.2   glutamic acid                                                (CH.sub.3).sub.2 CH.sub.2                                                                      valine                                                        ##STR9##        phenylalanine                                                 ##STR10##       tyrosine                                                      ##STR11##       histidine                                                     ##STR12##       tryoptophan                                                  H.sub.3 N(CH.sub.2).sub.3 CH.sub.2                                                             lysine                                                       H.sub.3.sup.+NCH.sub.2 (OH)CH.sub.2 CH.sub.2                                                   hydroxylysine                                                 ##STR13##       arginine                                                     ______________________________________                                    

The novel compositions of this invention may be combined with a majoramount of a suitable lubricating oil to provide novel lubricatingcompositions. Said novel lubricating compositions have extreme pressure,anti-wear, friction reducing, corrosion inhibition and anti-oxidationproperties. The novel compositions of this invention are preferablyused, at a concentration ranging from about 0.0001 to about 10 percent,more preferably, from about 0.01 to about 1 percent, e.g. about 0.04percent, by weight, as additives in a wide variety of lubricating oils,for example, mineral oil, (including automobile engine oil), syntheticoil, industrial oils, for example, cutting oil, metal working fluids andgrease. In addition, the additives may be added to lubricating oilsderived from paraffins, naphthenic or mixed base crude petroleum oils,that have been subject to solvent and/or sulfuric-acid treatment,aluminum chloride treatment, hydrogenation and/or other refiningtreatments.

Preferred distillate lubrication oils which are improved by the additionof the additives herein have an initial boiling point within the rangeof 350° F. to about 475° F., an end point in the range of about 500° F.to about 1,100° F., and a flash point not lower than 110° F.

Lubricants derived from oil shale are particularly suitable forincorporation of the above novel compositions therein. Oil shale isbroadly defined as a variety of compact sedimentary rock, generallylaminated, that contains little or no oil but does contain organicmaterial, derived from aquatic organisms or waxy spores and pollengrains, which is convertible to oil by heat. Crude shale oil, incombination with water, gas and spent shale containing a carbonaceousresidue and mineral matter, is formed by the pyrolysis of oil shale. Thehydrocarbons of shale oil are highly unsaturated, resembling theproducts of thermal cracking of petroleum, as would be expected becauseof the pyrolytic origin of shale oil. Once the shale oil is extracted,it is subjected to conventional hydrotreating procedures to produce avariety of hydrocarbon products, including lubricants.

Synthetic lubricating oils useful herein are those oils derived from aproduct of chemical synthesis (man-made oils). Typical examples of suchcompositions include the polyglycol fluids (i.e., polyalkylene glycol);silicones which consist of a silicone-oxygen polymer chain to which areattached hydrocarbon branches composed of either alkyl or phenyl groups;phosphates; polyphenyl esters; synthetic hydrocarbons and various estersof organic acids and alcohols.

The polyalkylene glycol lubricating oils suitable for use hereinpreferably are derived from the reaction product of the appropriatealkylene oxides. The alkylene moiety of the above compositions have acarbon chain of from about 1 to about 10 carbon atoms. The polyalkyleneglycol may preferably comprise from about 200 to about 1,000 carbonatoms, most preferably from about 200 to about 800 carbon atoms.Representative examples of suitable polyalkylene glycols include,polyethylene glycol, polypropylene glycol, polyisopropylene glycol,polybutylene glycol and the like.

Synthetic lubricating oils derived from hydrocarbons are generally oftwo types, namely dialkylated benezene and polymerized alpha-olefins.Dialkylated benzene herein is formed from the condensation product ofthe appropriate alkyl compound and has a carbon chain from about 5 toabout 50 carbon atoms, preferably from about 8 to about 20 carbon atoms;and a molecular weight of from about 200 to about 1,500, preferably fromabout 300 to about 700. Representative compounds includedi-n-decylbenzene, n-decyl-n-tetradecylbenzene, andn-nonyl-n-dodecylbenzene.

Alpha-olefins suitable for use in preparing lubricating oils herein arecharacterized by the formula R⁴ CH=CH₂ wherein R⁴ is a radical selectedfrom the group of hydrogen and alkyl radicals having about 4 to about 18carbon atoms, preferably from about 6 to about 10 carbon atoms, andhaving a molecular weight of from about 80 to about 300, preferably fromabout 100 to about 200. Typical compounds include 1-octene, 1-decene and1-dodecene.

Phosphates suitable for use herein as synthetic lubricating oils are thephosphate esters having the formula 0=P(OR⁵)₃, wherein R⁵ is aryl oralkyl having from about 4 to about 20 carbon atoms, preferably from 6 toabout 10 carbon atoms, and have a molecular weight within the range offrom about 200 to about 1,000, preferably from about 300 to 550.Representative compounds include trioctyl phosphate, tricresyl phosphateand dicresyl methyl phosphate.

Esters of organic acids which are suitable for use herein are syntheticlubricating oils preferably are selected from organic acids havingcarbon chains of from 4 to 40 carbon atoms. Organic acids which may bereacted with the alcohols herein include caproic, decanoic, sebacic,laurel, oleic, stearic, palmitic, etc. Likewise, alcohols herein may beeither natural or synthetic in origin, for example, pentaerythritol,trimethylolpropane, amyl, 2-ethyl-hexanol or lauryl alcohol, may be usedto form the desired ester. The esters are formed using conventionalmethods. For example, the esters may be prepared by reaction of thedesired alcohol with the desired acid, acid anhydride or acid halideusing conventional reaction conditions and techniques.

If desired, the compositions of the present invention may be employed inconjection with other additives commonly used in petroleum products.Thus, there may be added to the oil compositions of this invention rustinhibitors, emulsifying agents, dyes, haze inhibitors, anti-staticagents, detergents, dispersants, viscosity index improvement agents,pour point reducing agents, other extreme pressure additives, corrosioninhibitors and oxidation inhibitors, Soaps or other thickening agentsmay be added to the lubricating oil compositions to form compositionshaving the consistency of grease.

The invention is further illustrated by the following examples which areillustrative of a specific mode of practicing the invention and are notintended as limiting the scope of the appended claims.

EXAMPLE 1

This example illustrates the preparation of the novel compositions ofthe present invention wherein R² =H and R=nonyl. A mixture of water (64ml), glycine (15 g) and KOH (4 g) is adjusted to a pH of 8 with 1M HCl.A solution of formaldehyde (36.5 g of 37% formaldehyde in water) and KOH(4 g) is then added to the above mixture over a 40 minute period toprovide a reaction mixture. Methanol (600 ml) is added as a cosolvent,to the reaction mixture and the pH is adjusted to 7.5. A mixture ofnonylphenol (65.4 g) and methanol (200 ml) is then added over a periodof two hours to the cosolvent-containing reaction mixture. During thefirst 1/2 hour the cosolvent-containing reaction mixture is heated to56° C. and held at that temperature throughout the addition. After theaddition is complete the temperature of the resulting mixture iselevated to 72°-73° C. and refluxed for 3.5 hours. The mixture is thenslowly cooled to room temperature and the phases are allowed toseparate. The organic layer is separated and dried leaving a powderysolid (81.4 g). The pure composition is extracted from the solid byacetonitrile to provide a potassium salt.

Cupric acetate (2.0 g, 0.01 mole) and the above potassium salt (10 g,0.01 mole) are added to 50 ml of n-butyl ether. The mixture is refluxedfor 4 hours. Afterwards the mixture is filtered, and the organicsolution is washed with water and saturated aqueous sodium chloridesolution. After drying over potassium carbonate, rotary evaporationyields 9.0 g of the copper salt.

The zinc, lead, manganese, cobalt and iron salts are made using asimilar procedure except that the appropriate metal acetate issubstituted for cupric acetate. These salts as well as the sodium salt(made by replacing KOH with NaOH and carrying out the first two steps ofthe above reaction) are tested as dispersants for lubricating oils inExample II, below.

EXAMPLE II

The organometallic compositions of the present invention, prepared as inExample I, are blended into lubricating oil at the concentrations givenbelow and tested in the Cincinnati Millicaron Thermal Stability Test(CMTS Test). The amount of sludge that forms during the test is given inTable I. To carry out the CMTS test, a 250-ml beaker with 100 ml ofblend and solid steel and copper rods are placed in an oven at 135° C.for 168 hours. The CMTS test quantifies oil degradation throughviscosity increase, D-664A neutralization number increase, copper rodweight loss/appearance, steel rod weight loss/appearance, and totalsludge. In a vast majority of the cases, if the total sludge is below 25mg, the CMTS specification maximum, the rest of the CMTS results meetspecification. Thus, only the CMTS sludge result is reported.

    ______________________________________                                                               Cincinnati                                                                    Milacron                                               Component      wt. %.sup.a.                                                                          Sludge, mg/100 ml                                      ______________________________________                                        --             --      20.8                                                   Zinc Salt      0.04%   8.4                                                    Lead Salt      0.04%   17.7                                                   Sodium Salt    0.005%  4.8                                                    Manganese Salt 0.04%   5.7                                                    Cobalt Salt    0.04%   8.5                                                    Copper Salt    0.04%   8.4                                                    Iron Salt      0.04%   8.7                                                    ______________________________________                                         .sup.a. All blends contain 0.38 wt. % Ethyl 735 (2,6di-tert-butyl phenol)     in 150 neutral base stock.                                               

As can be seen by the above the sludge is reduced by addition of thevarious metal salts of this invention. In particular, the manganese saltis effective as a dispersant as compared to the control.

EXAMPLE III

Certain of the compositions of this invention, prepared as in Example I,are tested for oxidative stability by use of the Penn StateMicrooxidation Test. In this test a flat bottom glass tube containing ametal disc with a lip is used. A thin film of oil is placed on top ofthe metal disc. The thickness of the oil film is usually about 0.01 cmfor normal operating conditions. To provide isothermal conditions, theglass tube is submerged in a constant temperature bath, which is anelectrically heated aluminum block filled with low melting alloy. Thetest is run at 400° F.

The oil is oxidized for a fixed period of time in this test. After thetest, the oxidized sample is cooled and dissolved in tetrahydrofuran(THF). The dissolved sample is analyzed by gel permeation chromatography(GPC) to determine the molecular weight distribution of the sample. Themolecular weight distribution of the oxidized oil is a good measure ofthe degree of thickening.

The compositions of this invention are compared to other additives andthe results reported in Table II. The additives are mixed at 0.5, 1.0and 2.0 weight percent in 150 Neutral base oil. The resulting mixturesare then treated with 100 ppm of iron naphthenate, since iron, which isfound in used engine oils, is believed to catalyze polymerization ofinitially oxidized products in oil. The iron-treated mixtures are heatedto 400° F. for 40 minutes and then analyzed by gel permeationchromatography (GPC) for relative amounts of HMWP (products havingmolecular weight greater than 1000). The copper salt performs slightlybetter than the cobalt, sodium, magnesium and manganese salts. It can,also, be readily seen that the magnesium and manganese salts reduce HMWPformation of the 150 Neutral base oil.

                  TABLE II                                                        ______________________________________                                        Relative Amounts of HMWP Formed in 150 Neutral                                Containing Various Additives After Microoxidation Testing                                    Weight Percent of Additive                                                    in 150 Neutral Base Stock                                      Additive Description                                                                           0.5      1.0        2.0                                      ______________________________________                                        1.  None             6.2                                                      2.  Copper salt      1.7      1.1      2.2                                    3.  Elco 106, ZnDDP.sup.a                                                                          8.7      2.2      1.7                                    4.  Elco 108, ZnDDP.sup.a                                                                          2.2      2.6      2.4                                    5.  Elco L-28643, ZnDDP.sup.a                                                                      1.8      4.8      2.3                                    6.  Elco L-34132, ZnDDP.sup.a                                                                      3.7      3.6      1.2                                    7.  Lz 894, dispersant.sup.b                                                                       --       --       5.7                                    8.  Lz 936, dispersant.sup.c                                                                       10.7     --       7.2                                    9.  Lz 6575, Zn dispersant.sup.d                                                                   --       4.9      6.7                                    10. ECI 644, dispersant.sup.e                                                                      --       --       3.9                                    11. ECI 645, dispersant.sup.e                                                                      --       7.0      5.2                                    12. Cobalt salt      --       4.8      1.7                                    13. Sodium salt      --       2.6      0.9                                    14. Magnesium salt   --       3.0      4.1                                    15. Manganese salt   --       4.9      6.7                                    ______________________________________                                         .sup.a Zinc bis(dialkyldithiophosphates) available from                       .sup.b Polyalkenylsuccinaminade available from the Lubrizol Corporation.      .sup.c Nonnitrogen-containing dispersant of the polyestertype available       from the Lubrizol Corporation                                                 .sup.d Zinc-containing dispersant available from the Lubrizol                 .sup.e Polyalkenylsuccinamides available from the Ethyl Petroleum             Additives Division of the Ethyl Corporation                              

EXAMPLE IV

The compositions of the instant invention are tested for rust-inhibitionproperties when utilized in a lubricating oil composition by ASTM D-665.The results are reported in Table III below.

                  TABLE III                                                       ______________________________________                                        ASTM D-665 PROCEDURE A RUST INHIBITION TEST OF                                VARIOUS BLENDS CONTAINING THE                                                 COMPOSITIONS OF THIS INVENTION                                                Sample                 ASTM D-665 A                                           Number Composition     %       TEST RESULT                                    ______________________________________                                               ALUMINUM SALT                                                          1      Aluminum salt   0.2     Fail after 24 hours                                   150 Neutral     99.8    with 2% rust                                   2      Aluminum salt   0.1     Fail after 24                                         VL 81.sup.(a)   1.0     hours                                                 150 Neutral     98.9                                                   3      Aluminum salt   0.10    Fail after 24 hours                                   Ethyl 735       0.38                                                          150 Neutral     99.52                                                         BARIUM SALT                                                            4.     Barium salt     0.70    Pass                                                  Ethyl 735       0.38                                                          150 Neutral     98.92                                                  5.     Barium salt     0.70    Pass                                                  VL 81           1.00                                                          150 Neutral     98.30                                                  6.     Barium salt     0.20    Pass                                                  Ethyl 735       0.38                                                          150 Neutral     99.42                                                  7.     Barium salt     0.20    Pass                                                  VL 81           1.00                                                          150 Neutral     98.80                                                  8.     Barium salt     0.10    Pass                                                  DCF 200.sup.(b) 5 ppm                                                         200 Neutral     99.9                                                   9.     Barium salt     0.10    Pass                                                  DCF 200         5 ppm                                                         100 Neutral     45.0                                                          200 Neutral     54.9                                                   10.    Barium salt     0.10    Pass                                                  DCF 200          5 ppm                                                        200 Neutral     51.9                                                          175 Bright Stock                                                       11.    Barium salt     0.10    Pass                                                  DCF 200         5 ppm                                                         200 Neutral     82.9                                                          175 Bright Stock                                                                              12.0                                                   12.    Barium salt     0.04    Pass                                                  Ethyl 735       0.38                                                          150 Neutral     99.58                                                         CALCIUM SALT                                                           13.    Calcium salt    0.70    Pass                                                  Ethyl 735       0.38                                                          100 neutral     98.92                                                  14.    Calcium salt    0.50    Pass                                                  Ethyl 735       0.38                                                          100 neutral     99.12                                                  15.    Calcium salt    0.20    Borderline                                            VL 81           1.00    Pass (1 spot)                                         150 neutral     99.58                                                  16.    Calcium salt    0.04    Fail after 24 hours                                   Ethyl 735       0.38                                                          150 neutral                                                                   COPPER SALT                                                            17.    Copper salt     0.2     Fail in two hours                                     VL 81           1.0     with 10% rust                                         150 Neutral                                                            18.    Copper salt     0.04    Fail in one hour                                      Lz 677A.sup.(c) 0.70                                                          150 Neutral     99.26                                                         IRON SALT                                                              19.    Iron salt       0.2     Fail in one hour                                      VL 81           1.0                                                           150 Neutral     98.8                                                          LEAD SALT                                                              20.    Lead salt       0.2     Fail in two hours                                     VL 81           1.0     with 10% rust                                         150 Neutral     98.8                                                          MAGNESIUM SALT                                                         21.    Magnesium salt  0.04    Fail after 24 hours                                   Ethyl 735       0.38                                                          150 Neutral     99.68                                                  22.    Magnesium salt  0.04    Fail after three                                      VL 81           1.00    hours with 5% rust                                    150 Neutral     98.96                                                  23.    Magnesium salt  0.2     Pass                                                  VL 81           1.0                                                           150 Neutral     98.8                                                   24.    Magnesium salt  0.20    Pass                                                  Ethyl 735       0.38                                                          150 Neutral     99.42                                                         MANGANESE SALT                                                         25.    Manganese salt  0.20    Fail in 24 hours                                      VL 81           1.00    with 4-6 spots                                        150 Neutral     98.80                                                         POTASSIUM SALT                                                         26.    Potassium salt  0.04    Pass                                                  150 Neutral     99.96                                                  27.    Potassium salt  0.1     Pass                                                  150 Neutral     99.9                                                   28.    Potassium salt  0.7     Pass                                                  150 Neutral     99.3                                                          SODIUM SALT                                                            29.    Sodium salt     0.7     Pass                                                  Lz 677A         0.7                                                           150 Neutral     98.6                                                   30.    Sodium salt     0.2     Fail at 24 hours                                      VL 81           1.0                                                           150 Neutral 98.8                                                              ZINC SALT                                                              31.    Zinc salt       0.04    Fail after four                                       Ethyl 735       0.38    hours                                                 150 Neutral     99.58                                                  32.    Zinc salt       0.2     Fail in one hour                                      VL 81           1.0                                                           150 Neutral     98.8                                                   33.    Zinc salt       1.0     Fail in one hour                                      VL 81           1.0     about 50% rust                                        150 Neutral     98.0                                                   34.    150 Neutral     100.0%  Fail in less than                                                             one hour                                       35.    Armeen 18D.sup.(D)                                                                            2.0     Fail in less than                                     150 Neutral     98.0    one hour                                       36.    Ethyl 735       0.38    Fail in less than                                     150 Neutral             one hour                                       37.    VL 81           1.0     Fail in less than                                     150 Neutral     99.0    one hour                                       ______________________________________                                         Footnotes-                                                                    .sup.(A) Diphenylamine antioxidant                                            .sup.(B) A silicone antifoamant-                                              .sup.(C) Zinc                                                                 .sup.(D) Primary amine rust inhibitor                                    

These results show that the calcium, magnesium and barium salts are veryeffective in preventing rust in the ASTM D665 Procedure A.

EXAMPLE V

Certain of the compositions of the instant invention are evaluated asanti-wear additives for lubricating oils by means of the Four-Ball WearTest. The lubricating oil compositions tested comprise 1 percent, byweight, of the compositions of the instant invention, prepared accordingto Example 1, in 150 Neutral oil. The results, as may be seen from TableIV, below, indicate that the magnesium, manganese, zinc and calciumsalts significantly improve the anti-wear properties of the lubricatingoil

                  TABLE IV                                                        ______________________________________                                        Four-Ball Wear Test.sup.a                                                                    Treat Rate of                                                                             Ball Scar                                                                              Average                                                  Additive in 150                                                                           Diameter Scar                                      Additive       wt %        mm       mm.sup.2                                  ______________________________________                                        1.  None (150 Neutral)                                                                           --          0.77   0.60                                    2.  Elco 106       1.0         0.38   0.14                                    3.  Elco 108       1.0         0.40   0.16                                    4.  Cobalt salt    0.5         0.55   0.30                                    5.  Cobalt salt    1.0         0.33   0.11                                    6.  Cobalt salt    2.0         0.32   0.11                                    7.  Sodium salt    1.0         0.51   0.27                                    8.  Manganese salt 1.0         0.52   0.29                                    9.  Copper salt    1.0         0.60   0.36                                    10. Zinc salt      1.0         0.71   0.48                                    11. Magnesium salt 1.0         0.53   0.28                                    12. Calcium salt   1.0         0.50   0.26                                    13. Potassium salt.sup.(b)                                                                       1.0         0.49   0.26                                    ______________________________________                                         .sup.a Test Conditions: Speed 600 rpm; Load 40 kg; Test time, 1 hour; Tes     temperature 167° F.                                                    .sup.b Made according to the procedure of Example 1 by substituting           aspartic acid for glycine. (R.sup.2 = HOOCCH.sub.2 --).                  

EXAMPLE VI

Various novel organo metallic compositions are prepared and the amountof chelated metal determined. A disodium salt of an organic chelatehaving the above general formula wherein R is nonyl, R² and R³ arehydrogen, x is 2 and w is 0 is contacted with the appropriate metalacetate in a toluene solution under reaction conditions. The resultingacetic acid is azeotropically distilled from the reaction mixture toobtain the novel organometallic composition. The yield and percent metalof each organometallic composition is reported in Table V below. Notethat the manganese chelate unexpectedly contains more than the predictedmetal content.

                                      TABLE V                                     __________________________________________________________________________                                           % Metal                                Amount of                                                                           Type of    Amount of             Product                                Chelate                                                                             Metal      Acetate                                                                             Amount of                                                                            Yield g  results/                               g (mole)                                                                            Acetate    g (mole)                                                                            Toluene,ml                                                                           (moles)                                                                           Yield %                                                                            predict.                               __________________________________________________________________________    10    cobalt     2.90  250    9.64                                                                              91   6.49/6.42                              (0.0116)                                                                            acetate    (0.0116)     (0.105)                                         10    cupric     2.12  250    10.32                                                                             97   5.77/6.89                              (0.0116)                                                                            acetate    (0.0116)     (0.0112)                                        10    zinc       2.56  250    9.46                                                                              89   6.55/7.08                              (0.0116)                                                                            acetate    (0.0116)     (0.0103)                                        10    lead       4.42  250    10.89                                                                             88   5.7/19.5                               (0.0116)                                                                            acetate    (0.0116)     (0.0102)                                        10    nickel     2.90  250    7.47                                                                              73   0.17/6.40                              (0.0116)                                                                            acetate    (0.0116)     (0.0082)                                        10    manganese  2.02  250    8.60                                                                              82   8.22/6.01                              (0.0116)                                                                            acetate    (0.0116)     (0.0094)                                        10    iron       2.03  250    9.52                                                                              90   4.84/6.11                              (0.0116)                                                                            acetate    (0.0116)     (0.0104)                                        10    aluminum   (0.0116)                                                                            250    --  --   4.22/7.13                              (0.0116)                                                                            acetate (basic)                                                               [Al(OOCCH.sub.3)(OH)]                                                   __________________________________________________________________________

While particular embodiments of the invention have been described, itwill be understood, of course, that the invention is not limited theretosince many obvious modifications can be made, and it is intended toinclude within this invention any such modifications as will fall withinthe scope of the appended claims.

I claim:
 1. A composition of matter represented by the general formula:##STR14## wherein M is selected from the group consisting of members ofGroups IIa, IIb, IIIa, IVa and VIIb of the Periodic System of Elements;R¹ is selected from the group consisting of radicals represented by theformula ##STR15## wherein R² is selected from the group consisting ofhydrogen, hydrocarbyl radicals and heteroatom-substituted hydrocarbylradicals wherein said heteroatoms are selected from the group consistingof halogen, oxygen, sulfur, nitrogen and phosphorus atoms; R³ isselected from the group consisting of hydrogen and lower alkyl radicals;R is selected from the group consisting of hydrocarbyl radicals andhetero atom-substituted derivatives thereof wherein said heteroatoms areselected from the group consisting of halogen, oxygen, sulfur, nitrogenand phosphorus atoms; and v, w, x, y and z are integers, except thatwhen x is zero at least one w is
 1. 2. The composition of claim 1wherein M is selected from the group consisting of Mg, Ca, Ba, Zn, Al,Pb and Mn.
 3. The composition of claim 2 wherein R is selected from thegroup consisting of hydrocarbyl radicals having from about 3 to 1000carbon atoms.
 4. The composition of claim 3 wherein R² is selected fromthe group consisting of hydrogen, a lower alkylgroup, ##STR16##
 5. Thecomposition of claim 4 wherein R² is hydrogen.
 6. The composition ofclaim 4 wherein R² is HOOCCH₂ -
 7. The composition of claim 5 wherein Mis Mg.
 8. The composition of claim 5 wherein M is Ba.
 9. The compositionof claim 5 wherein M is Zn.
 10. The composition of claim 5 wherein M isMn.
 11. The composition of claim 5 wherein M is Ca.
 12. A lubricatingoil composition comprising a lubricating oil and the composition ofclaim 7 or 8 in rust-inhibiting effective amount.
 13. A lubricating oilcomposition comprising a lubricating oil and the composition of claim 10in a sludge-dispersing effective amount.
 14. A lubricating oilcomposition comprising a lubricating oil and the composition of claims7, 9, 10 or 11 in a wear-reducing effective amount.
 15. A lubricatingoil composition comprising a lubricating oil and the composition ofclaims 7 or 10 in an anti-oxidant effective amount.
 16. A lubricatingoil composition comprising a lubricating oil and the composition ofclaim 1 in rust-inhibiting effective amount.
 17. A lubricating oilcomposition comprising a lubricating oil and the composition of claim 1in a sludge-dispersing effective amount.
 18. A lubricating oilcomposition comprising a lubricating oil and the composition of claims 1in a wear-reducing effective amount.
 19. A lubricating oil compositioncomprising a lubricating oil and the composition of claim 1 in ananti-oxidant effective amount.
 20. A method for preparing aorganometallic composition, useful as a lubricating oil additive, whichcomprises the steps of:(a) reacting formaldehyde with an alpha-aminoacid in an basic aqueous solution; (b) reacting the product of step (a)with a phenolic compound to provide an organo compound comprisinghydroxyl and alpha-aminocarboxyl groups, and (c) reacting the product ofstep (b) with a metal salt comprising a metal ion selected from thegroup consisting of members of Groups IIa, IIb, IIIa, IVa, and VIIIb ofthe Periodic System of the Elements to provide an oil-solubleorganometallic composition comprising said metal ion.
 21. The method ofclaim 20 wherein said alpha-amino acid is of the general formula NH₂ CR²R³ COOH wherein R² is selected from the group consisting of hydrogen,hydrocarbyl radicals and heteroatom-substituted hydrocarbyl radicalswherein said heteroatoms are selected from the group consisting ofhalogen, oxygen, sulfur, nitrogen and phosphorus atoms; and R³ isselected from the group consisting of hydrogen and lower alkyl radicals.22. The method of claim 21 wherein said phenolic compound is of thegeneral formula ##STR17## and R is selected from the group consisting ofhydrocarbyl radicals and hetero atom-substituted derivatives thereofwherein said heteroatoms are selected from the group consisting ofhalogen, oxygen, sulfur, nitrogen and phosphorus atoms.
 23. The methodof claim 22 further comprising carrying out step (b) in the presence ofan alcohol cosolvent.
 24. The method of claim 23 wherein said product ofstep (b) is separated from its reaction mixture as a solid product. 25.The method of claim 24 wherein said solid product is reacted with saidmetal salt in the presence of a refluxing organic solvent.
 26. Themethod of claim 25 wherein said organic solvent is an ether.
 27. Acomposition prepared according to the method of claims 20, 21, 22, 23,24, 25, or
 26. 28. A lubricating oil composition comprising thecomposition of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or
 11. 29. Alubricating oil composition comprising the composition of claim 27.